Nickel Complexes of Allyl and Vinyldiphenylphosphine

Monodentate phosphine-ligated nickel compounds, e.g., [Ni(PPh3)4] are relevant as active catalysts across a broad range of reactions. This report expands upon the coordination chemistry of this family, offering the reactivity of allyl- and vinyl-substituted diphenylphosphine (PPh2R) with [Ni(COD)2] (COD = 1,5-cyclooctadiene). These reactions provide three-coordinate dinickelacycles that are intermolecularly tethered through adjacent {Ni}-olefin interactions. The ring conformation of such cycles has been studied in the solid-state and using theoretical calculations. Here, a difference in reaction outcome is linked to the presence of an allyl vs vinyl group, where the former is observed to undergo rearrangement, bringing about challenges in clean product isolation.单齿膦配体配位的镍化合物（Monodentate phosphine-ligated nickel compounds），例如[Ni(PPh3)4]，可作为活性催化剂广泛应用于各类反应中。本研究拓展了该类配合物的配位化学研究范畴，报道了烯丙基取代与乙烯基取代二苯基膦（PPh2R）分别与[Ni(COD)2]（COD=1,5-环辛二烯）的反应活性。此类反应可生成三配位二镍杂环，该类杂环通过相邻的{Ni}-烯烃相互作用实现分子间拴连。已通过固态表征与理论计算对该类杂环的环构象展开了研究。本研究发现，反应产物的差异与取代基为烯丙基还是乙烯基密切相关：其中烯丙基取代底物会发生重排反应，给纯净产物的分离带来了挑战。